CN106188143A - A kind of phosphorous, nitrogen combustion inhibitor and preparation method thereof - Google Patents
A kind of phosphorous, nitrogen combustion inhibitor and preparation method thereof Download PDFInfo
- Publication number
- CN106188143A CN106188143A CN201610548989.9A CN201610548989A CN106188143A CN 106188143 A CN106188143 A CN 106188143A CN 201610548989 A CN201610548989 A CN 201610548989A CN 106188143 A CN106188143 A CN 106188143A
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- China
- Prior art keywords
- phosphorous
- combustion inhibitor
- nitrogen combustion
- preparation
- inhibitor preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
Abstract
A kind of phosphorous, nitrogen combustion inhibitor and preparation method thereof, relate to a kind of chemosynthesis agent and preparation method thereof, the present invention prepares raw material and includes: 3 amino phenols, glutaraldehyde and 9,10 dihydros 9 oxa-10 phospho hetero phenanthrene 10 oxide (DOPO), the method preparing this fire retardant is divided into two steps to carry out, 3 amino phenols are reacted a kind of Schiff's base (Schiff base) intermediate of generation under certain condition by the first step with glutaraldehyde；Second step, by first step gained intermediate and DOPO stirring reaction certain time under noble gas imports, product, through process such as filtering, wash, be dried, obtains yellow-brown solid powder.Present invention process working condition is simple, product purity and productivity is higher, last handling process is easy.
Description
Technical field
The present invention relates to a kind of chemosynthesis agent and preparation method thereof, particularly relate to a kind of phosphorous, nitrogen combustion inhibitor and
Preparation method.
Background technology
The problem of Halogen material environmental pollution is the problem that current fire-retardant academia is the most popular, for halogenated flame retardant
Find suitable substitute products and the most also become the important research direction of fire-retardant academic worker.Along with material combustion product is divided
Analysis research, a large amount of scholars think, have the release of two English or dibenzofurans during halogenated flame retardant burning.Due to currently without
Enough succedaneum carry out replacing whole halogen containing flame-retardant, and Europe and Japan have completely forbidden the use of halogen containing flame-retardant simultaneously.
Subsequently, relevant electronic electric equipment treatment of wastes produced specification has been promulgated in Europe, it is stipulated that halogen system refuse needs to carry out special handling, this
On the one hand the use of halogen-free flame retardants has been promoted.
The research direction of fire retardant increasingly tends to non-halogen.How to replace halogen, develop efficient, low toxicity, low cigarette or nothing
The halogen-free environment-friendly type flame-proof agent of cigarette becomes the study hotspot of Chinese scholars.
Summary of the invention
It is an object of the invention to provide a kind of phosphorous, nitrogen combustion inhibitor and preparation method thereof, raw material of the present invention contains phosphorus, nitrogen
Two kinds of ignition-proof elements, are a kind of halogen-free flame retardants, meet the requirement that current people preserve the ecological environment.
It is an object of the invention to be achieved through the following technical solutions:
A kind of phosphorous, nitrogen combustion inhibitor, described phosphorus, nitrogen combustion inhibitor raw material include: 3-amino phenols, glutaraldehyde and 9,10-dihydro-9-
Oxa--10-phospho hetero phenanthrene-10-oxide (DOPO), fire retardant has a structure that
。
A kind of phosphorous, nitrogen combustion inhibitor preparation method, the preparation method of this fire retardant is that two steps are carried out, the first step, will
3-amino phenols reacts the intermediate generated containing-C=N-structure in a solvent with glutaraldehyde；Second step, by intermediate with DOPO lazy
Property gas import under stir reaction, product through filter, washing, dried, obtain yellow-brown solid powder；
Said process chemical equation is expressed as:
。
Described one is phosphorous, nitrogen combustion inhibitor preparation method, in first step synthesis Shiff base intermediate, and glutaraldehyde
It is 1:2 to 1:4 with 3-amino phenols molar ratio；Solvent for use is the mixing of a kind of or its arbitrary proportion in methanol, ethanol
Thing.
Described one is phosphorous, nitrogen combustion inhibitor preparation method, in first step synthesis Shiff base intermediate, and reaction temperature
Degree controls at 20 ~ 70 DEG C；Response time is 3 ~ 12h.
Described one is phosphorous, nitrogen combustion inhibitor preparation method, in second step, noble gas used be nitrogen, argon or
One in helium.
Described one is phosphorous, nitrogen combustion inhibitor preparation method, in second step, react use Isosorbide-5-Nitrae-dioxane, benzene,
N, is carried out under any one solvent condition in N '-dimethyl Methanamide.
Described one is phosphorous, nitrogen combustion inhibitor preparation method, and in second step, reaction temperature is 60 ~ 110 DEG C.
Described one is phosphorous, nitrogen combustion inhibitor preparation method, and in second step, the response time is 6 ~ 24h.
Described one is phosphorous, nitrogen combustion inhibitor preparation method, in second step, cleaning solvent be Isosorbide-5-Nitrae-dioxane, benzene,
N, the mixture of any one or its arbitrary proportion in N '-dimethyl Methanamide.
Described one is phosphorous, nitrogen combustion inhibitor preparation method, and in second step, baking temperature is 80 ~ 120 DEG C.
Advantages of the present invention with effect is:
1, the one that the present invention provides is phosphorous, nitrogen combustion inhibitor, the advantage with low toxicity, environmental protection, beneficially sustainable development.
2, the preparation method that the present invention provides is simple, mild condition, it is easy to control, and the product purity of gained is high, post processing
Convenient.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
The first step: to equipped with reflux condensing tube, thermometer, N2The 500ml there-necked flask of ingress pipe and magneton adds 300ml ethanol
As solvent, add 33.0g3-amino phenols, under room temperature, 60g glutaraldehyde (25% solution) is slowly dropped in flask.It is passed through
N2Protection, insulation reaction 6h.Reaction carries out filtering after terminating, washs, after drying, obtain red brown solid powder, be Shiff
Base intermediate.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 250ml four-hole bottle of ingress pipe and thermometer adds
150ml1,4-dioxane, as solvent, adds 8.3gShiff base intermediate and 18.0gDOPO, after 60 DEG C of reaction 1h
It is warming up to 90 DEG C, insulation reaction 5h, terminates reaction, through filtering, washing, is dried to obtain yellow-brown solid powder.
Embodiment 2:
The first step: the synthetic method of Shiff base intermediate is with embodiment 1.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 250ml four-hole bottle of ingress pipe and thermometer adds
150ml1,4-dioxane, as solvent, adds 8.3gShiff base intermediate and 18.0gDOPO, after room temperature reaction 1h
It is warming up to 100 DEG C, insulation reaction 6h, terminates reaction, through filtering, washing, is dried to obtain yellow-brown solid powder.
Embodiment 3:
The first step: the synthetic method of Shiff base intermediate is with embodiment 1.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 250ml four-hole bottle of ingress pipe and thermometer adds
150ml1,4-dioxane, as solvent, adds 8.3gShiff base intermediate and 24.0gDOPO, after 50 DEG C of reaction 1h
It is warming up to 100 DEG C, insulation reaction 10h, terminates reaction, through filtering, washing, is dried to obtain yellow-brown solid powder.
Embodiment 4:
The first step: the synthetic method of Shiff base intermediate is with embodiment 1.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 250ml four-hole bottle of ingress pipe and thermometer adds
100ml1,4-dioxane, as solvent, adds 6.3gShiff base intermediate and 14.4gDOPO, after room temperature reaction 1h
It is warming up to 80 DEG C, insulation reaction 12h, terminates reaction, through filtering, washing, is dried to obtain yellow-brown solid powder.
Embodiment 5:
The first step: the synthetic method of Shiff base intermediate is with embodiment 1.
Second step: equipped with magnetic agitation, Dropping funnel, N2The 500ml four-hole bottle of ingress pipe and thermometer adds
300ml1,4-dioxane, as solvent, adds 25.0gShiff base intermediate and 59.4gDOPO, after 60 DEG C of reaction 1h
It is warming up to 100 DEG C, insulation reaction 20h, terminates reaction, through filtering, washing, is dried to obtain yellow-brown solid powder.
Claims (10)
1. phosphorous a, nitrogen combustion inhibitor, it is characterised in that described phosphorus, nitrogen combustion inhibitor raw material include: 3-amino phenols, glutaraldehyde
With 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), fire retardant has a structure that
。
2. phosphorous, a nitrogen combustion inhibitor preparation method, it is characterised in that the preparation method of this fire retardant is that two steps are carried out,
The first step, reacts 3-amino phenols to the intermediate generated containing-C=N-structure in a solvent with glutaraldehyde；Second step, by intermediate
With DOPO stirring reaction under noble gas imports, product, through filtration, washing, dried, obtains yellow-brown solid powder；
Said process chemical equation is expressed as:
。
One the most according to claim 2 is phosphorous, nitrogen combustion inhibitor preparation method, it is characterised in that synthesize in the first step
In Shiff base intermediate, glutaraldehyde and 3-amino phenols molar ratio are 1:2 to 1:4；Solvent for use is in methanol, ethanol
A kind of or mixture of its arbitrary proportion.
One the most according to claim 2 is phosphorous, nitrogen combustion inhibitor preparation method, it is characterised in that synthesize in the first step
In Shiff base intermediate, reaction temperature controls at 20 ~ 70 DEG C；Response time is 3 ~ 12h.
One the most according to claim 2 is phosphorous, nitrogen combustion inhibitor preparation method, it is characterised in that in second step, used
Noble gas is the one in nitrogen, argon or helium.
One the most according to claim 2 is phosphorous, nitrogen combustion inhibitor preparation method, it is characterised in that in second step, reaction
Using 1,4-dioxane, benzene, N, carrying out under any one solvent condition in N '-dimethyl Methanamide.
One the most according to claim 2 is phosphorous, nitrogen combustion inhibitor preparation method, it is characterised in that in second step, reaction
Temperature is 60 ~ 110 DEG C.
One the most according to claim 2 is phosphorous, nitrogen combustion inhibitor preparation method, it is characterised in that in second step, reaction
Time is 6 ~ 24h.
One the most according to claim 1 is phosphorous, nitrogen combustion inhibitor preparation method, it is characterised in that in second step, washing
Solvent is 1,4-dioxane, benzene, N, the mixture of any one or its arbitrary proportion in N '-dimethyl Methanamide.
One the most according to claim 2 is phosphorous, nitrogen combustion inhibitor preparation method, it is characterised in that in second step, dry
Dry temperature is 80 ~ 120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610548989.9A CN106188143A (en) | 2016-07-13 | 2016-07-13 | A kind of phosphorous, nitrogen combustion inhibitor and preparation method thereof |
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| CN201610548989.9A CN106188143A (en) | 2016-07-13 | 2016-07-13 | A kind of phosphorous, nitrogen combustion inhibitor and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739453A (en) * | 2017-11-14 | 2018-02-27 | 贵州省材料产业技术研究院 | DOPO derivative flame retardants and its preparation method and application |
| CN108864193A (en) * | 2017-05-09 | 2018-11-23 | 华中师范大学 | Phosphorus phenanthrene compound and its preparation method and application |
| CN110105395A (en) * | 2019-04-16 | 2019-08-09 | 皖西学院 | A kind of pyridine fire retardant and its preparation method and application |
| CN113248789A (en) * | 2021-07-09 | 2021-08-13 | 衡阳师范学院 | Inorganic-organic hybrid phosphorus-nitrogen-containing flame retardant, preparation method thereof and modified epoxy resin |
| CN114702817A (en) * | 2022-03-17 | 2022-07-05 | 广东华聚科技有限公司 | High-strength flame-retardant nylon and preparation process thereof |
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| CN101538283A (en) * | 2008-01-21 | 2009-09-23 | 长春人造树脂厂股份有限公司 | Oxazine compound and preparation method thereof |
| CN102838778A (en) * | 2012-10-09 | 2012-12-26 | 清华大学深圳研究生院 | Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof |
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Patent Citations (2)
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| CN101538283A (en) * | 2008-01-21 | 2009-09-23 | 长春人造树脂厂股份有限公司 | Oxazine compound and preparation method thereof |
| CN102838778A (en) * | 2012-10-09 | 2012-12-26 | 清华大学深圳研究生院 | Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof |
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| CONG XIE ET AL: "Improving Thermal and Flame-Retardant Properties of Epoxy Resins by a New Imine Linkage Phosphorous-Containing Curing Agent", 《POLYMER ENGINEERING & SCIENCE》 * |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864193A (en) * | 2017-05-09 | 2018-11-23 | 华中师范大学 | Phosphorus phenanthrene compound and its preparation method and application |
| CN108864193B (en) * | 2017-05-09 | 2023-08-04 | 华中师范大学 | Phosphaphenanthrene compound, and preparation method and application thereof |
| CN107739453A (en) * | 2017-11-14 | 2018-02-27 | 贵州省材料产业技术研究院 | DOPO derivative flame retardants and its preparation method and application |
| CN110105395A (en) * | 2019-04-16 | 2019-08-09 | 皖西学院 | A kind of pyridine fire retardant and its preparation method and application |
| CN113248789A (en) * | 2021-07-09 | 2021-08-13 | 衡阳师范学院 | Inorganic-organic hybrid phosphorus-nitrogen-containing flame retardant, preparation method thereof and modified epoxy resin |
| CN113248789B (en) * | 2021-07-09 | 2022-03-11 | 衡阳师范学院 | Inorganic-organic hybrid phosphorus-nitrogen-containing flame retardant, preparation method thereof and modified epoxy resin |
| CN114702817A (en) * | 2022-03-17 | 2022-07-05 | 广东华聚科技有限公司 | High-strength flame-retardant nylon and preparation process thereof |
| CN114702817B (en) * | 2022-03-17 | 2022-12-02 | 广东华聚科技有限公司 | High-strength flame-retardant nylon and preparation process thereof |
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